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Li2O (Lithium Oxide, Lithia)

Notes

-Lithium is the lightest, smallest, and most reactive flux. Adding small amounts by weight introduces disproportionately large amounts to the glaze formula (because of its low molecular weight).

-Together with boron and sodium, it acts as a melter at lower temperatures. Together with sodium and potassium oxides, it is classified as one of the Alkaline group.

-Lithium Carbonate, its main source, has a very low melting point and is a very active and powerful flux.

-In frits and glazes, lithia is used to reduce the viscosity and thereby increase the fluidity of the coatings. This reduces maturing times and lowers firing temperatures.

-1% additions can increase glaze gloss to a marked degree and slightly greater amounts (3%) can reduce melting temperature by several cones and affect surface tension of the melt.

-High cost limits its use in larger amounts, but in small amounts it acts as a powerful auxiliary alkaline flux with welcome thermal expansion lowering effects. However in large amounts lithia can drastically increase the thermal expansion of a glass.

-Calculated expansion projections tend to break down with all but low additions of lithium to glazes (less than 5%). Its contribution in nonlinear, especially in high sodium and potassium glazes. Often high lithium glazes appear to shiver whereas the calculated expansion does not indicate a sufficiently low expansion. It is known that molten lithia is mobile (diffuses into the surrounding matrix because of its small ionic radius and low charge). It can also diffuse into the body and create a low expansion glaze interface. One theory proposes that glazes with more than about 5 mol% Li2O could develop a lithium-rich interface (this could be coupled with a lithium-deficient upper glaze layer). The result could be crystallization of a spodumene layer thereby introducing its inversion and associated sudden expansion at 1082 C during cooling.

-Its expansion is much lower than soda or potash, and it is used to produce special low-expansion bodies and glazes which are resistant to heat-shock. When used as a partial substitute for sodium and potassium oxides, it produces glazes of lower expansion. But if it is simply added to a crazing glaze already containing significant KNaO, the crazing problem will not likely be fixed.

-Lithia gives the most intense colors in low alumina high alkali glazes.

-The alkalis can increase lead solubility.

-It can promote textural or variegated effects in the glaze surface because it promotes devitrifaction in glass systems.

-Lithia can promote bubble defects in glazes if used in isolation from the other alkalis.

-In some systems small additions of lithium will react with quartz during firing and can eliminate the alpha-beta quartz transition in the cooling cycle.

Lithia contributes to mottled and flow effects when used in small amounts (-1%).

Ceramic Oxide Periodic Table

All common traditional ceramic base glazes are made from only a dozen elements (plus oxygen). Materials decompose when glazes melt, sourcing these elements in oxide form. The kiln builds the glaze from these, it does not care what material sources what oxide (assuming, of course, that all materials do melt or dissolve completely into the melt to release those oxides). Each of these oxides contributes specific properties to the glass. So, you can look at a formula and make a good prediction of the properties of the fired glaze. And know what specific oxide to increase or decrease to move a property in a given direction (e.g. melting behavior, hardness, durability, thermal expansion, color, gloss, crystallization). And know about how they interact (affecting each other). This is powerful. And it is simpler than looking at glazes as recipes of hundreds of different materials (each sources multiple oxides so adjusting it affects multiple properties).

I am comparing 6 well known cone 6 fluid melt base glazes and have found some surprising things. The top row are 10 gram balls of each melted down onto a tile to demonstrate melt fluidity and bubble populations. Second, third, fourth rows show them on porcelain, buff, brown stonewares. The first column is a typical cone 6 boron-fluxed clear. The others add strontium, lithium and zinc or super-size the boron. They have more glassy smooth surfaces, less bubbles and would should give brilliant colors and reactive visual effects. The cost? They settle, crack, dust, gel, run during firing, craze or risk leaching. In the end I will pick one or two, fix the issues and provide instructions.

In pursuit of a reactive cone 6 base that I can live with

These melt-flow and ball-melt tests compare 6 unconventionally fluxed glazes with a traditional cone 6 moderately boron fluxed (+soda/calcia/magnesia) base (far left Plainsman G2926B). The objective is to achieve higher melt fluidity for a more brilliant surface and for more reactive response with colorant and variegator additions (with awareness of downsides of this). Classified by most active fluxes they are:
G3814 - Moderate zinc, no boron
G2938 - High-soda+lithia+strontium
G3808 - High boron+soda (Gerstley Borate based)
G3808A - 3808 chemistry sourced from frits
G3813 - Boron+zinc+lithia
G3806B - Soda+zinc+strontium+boron (mixed oxide effect)
This series of tests was done to choose a recipe, that while more fluid, will have a minimum of the problems associated with such (e.g. crazing, blistering, excessive running, susceptibility to leaching). As a final step the recipe will be adjusted as needed. We eventually chose G3806B and further modified it to reduce the thermal expansion.

The term 'limit formula' historically has typically referred to efforts to establish absolute ranges for mixtures of oxides that melt well at an intended temperature and are not in sufficient excess to cause defects. These formulas typically show ranges for each oxide commonly used in a specific gla...

On the theoretical glaze chemistry level, a flux is an oxide that lowers the melting or softening temperature of a mix of materials. Fluxes are interactors (they often melt poorly on their own but react strongly with high melting materials where Al2O3/SiO2 predominate). There are less than ten commo...